Aniline was used as a probe molecule to study energy transfer during laser-induced thermal desorption from a silica surface. Aniline is a substantially larger adsorbate than other molecules whose internal state distributions were previously studied following laser desorption and therefore poses some additional experimental challenges. Using resonance-enhanced multiphoton ionization spectroscopy, the internal energy of laser-desorbed aniline was measured to be T-vib = 360 +/- 60 K and T-rot = 350 +/- 100 K. The results are compared with calculated desorption temperatures of aniline from rapidly heated silica surfaces and are discussed in light of different mechanisms for laser-induced thermal desorption of large molecules from surfaces.